Particulate emulsifiable hair conditioning composition

ABSTRACT

The addition of up to 80 percent by weight of a fatty alcohol, and up to 10 percent by weight of a fatty alkylamido alkyldialkylamine to a quaternary ammonium compound, results in a particulate composition which, when stirred into warmed, slightly acidified water, almost immediately forms an emulsion. The emulsion thus produced overcomes many problems usually associated with the formulation of emulsions, and is suitable for use as a hair conditioner.

BACKGROUND OF INVENTION

1. Field of Invention

This invention relates to particulate compositions which readily formhair conditioning emulsions, when stirred into heated, acidified water.

2. Description of the Related Art

Modern hair cleansing agents, especially shampoos, while efficientlyremoving soil from the hair and scalp, simultaneously remove naturalprotective oils. Repeated use of shampoos (e.g. on a daily basis, not anuncommon practice in our society) may not allow sufficient time for thebody to replenish these protective natural oils. As a result, the hairbecomes dry, brittle, loses its natural sheen, builds up static electriccharges and is difficult to coif.

In order to overcome the deleterious effects of repeated hair washingsand permit hair to be clean, yet at the same time attractive, the arthas developed a spectrum of post-washing hair conditioning preparations.

Post-washing hair conditioning products well known to the art includecream rinses, spray conditioners, and setting lotions. It is also wellknown to the art that quaternary ammonium compounds are effectiveingredients in such hair conditioning preparations. They are believed tobe effective because they possess a positive electrostatic charge, whichis attracted to and neutralizes the negative charges of hair protein.The mutual attraction of opposite electrostatic charges thus causes thequaternary ammonium compound to tend to remain on the hair. Thistendency to remain on the hair is termed substantivity. Substantivequaternary ammonium compounds not only neutralize the electrostaticcharges of hair, but also may provide lubricity, by virtue of their longchain, (i.e. fatty) substituents.

Phenomena associated with quternary ammonium compounds in hairconditioning preparations are discussed for example in an article by T.G. Schoenberg "Role of Alkyl Amino Amine Salts in the Modern HairConditioner", Cosmetics and Toiletries, Volume 94, pages 57 et al(1979), which also includes detailed instructions for the preparation ofhair care formulations. Hair care formulations prepared with lanolinfatty acid quaternary ammonium compounds are described in "Effects ofthe Use of Lanolin Acid Quaternary in Human Hair ConditioningPreparations" by J. R. McCarthy and J. M. Laryea, Cosmetics andToiletries, Volume 94, pages 90 et al, (1979). U.S. Pat. No. 4,526,781teaches the use of betaines in hair care formulations. Betaines arequaternary ammonium compounds characterized by a zwitterionic structureand exemplified by the reaction product of sodium chloracetate with afatty dimethyl tertiary amine. The use of quaternary ammonium compoundsderived from halo-esters of fatty alcohols as hair conditioners istaught by U.S. Pat. No. 4,370,272. The preparation of a mixture ofquaternary ammonium compounds suitable for use in rinsing compositionsfor human hair is described in U.S. Pat. No. 3,803,137. U.S. Pat. No.3,211,646 teaches the antistatic properties of mixtures of fatty aciddimethylaminopropyl amides with quaternary ammonium compounds derivedfrom said dimethylaminopropyl amides.

Quaternary ammonium compounds are marketed to formulators as solutions,dispersions, and aqueous pastes. These materialsrequire bulky storageand handling facilities. They are more costly to ship than thesolvent-free quaternary ammonium compound, and present formulationdifficulties. Solutions and dispersions tend to lose solvent, thuschanging the concentration of quaternary ammonium compound dispensed.Sufficient loss of solvent or water may result in precipitation of thequaternary compound itself, leading to unequal distribution. Pastes arephysically difficult to dispense and suffer from the same loss ofsolvent problems as solutions and dispersions. In addition, pastes anddispersions tend to be difficult to emulsify. Quaternary ammoniumcompounds may be obtained as solids by evaporatively removing thesolvents; however, in their solid form, quaternary ammonium compoundsare even more difficult to disperse and emulsify than pastes ordispersions. The use of solid quaternary ammonium compounds mayintroduce variables into the formulation of hair care products becauseof the presence of variable quantities of residual water or solvents.

In addition to quaternary ammonium compounds, post-washing hair careformulations known in the art may include fatty alcohols and fattyalkylamido alkyldimethylamines, among others. Preparation, physicalcharacteristics and application in cosmetic chemistry of fattyamidoamine derivatives are described in an article by Muzyczko, et. al.(T. N. Muzyczko et. al. "Fatty Amidoamine Derivatives:N,N,-Dimethyl-N-(3 alkylamidopropyl) amines and their Salts."J.O.A.C.S., 45 Pg. 720-5 (1968). They may be prepared by reacting fattyacids with dialkyl amines. The fatty acids may be derived from naturallyoccuring fats and oils, and thus would have a chain length distributionfrom about C₈ to about C₂₂. Synthetic fatty acids may also be used. Thecombination of fatty alkylamido dimethylamines and a fattydialkylbenzylamonium chloride for use as a fabric softener is describedin German Patent number 2,224,508. A liquid detergent concentrate systempackaged for single use application as an industrial cleanser, includingfatty alcohols and quaternary ammonium compounds, is taught by U.S. Pat.No. 4,348,292. Thus, the prepackaged liquid concentrate is admixed withthe proper quantity of water to obtain a cleansing solution for hardsurfaces, bathrooms, and floors. The liquid concentrate taught by saidpatent consists of two immiscible layers within the same container.

SUMMARY OF THE INVENTION

We have discovered a particulate composition containing a quaternaryammonium compound, which may be used for the preparation of post-washinghair conditioning emulsions. Thus, the addition of the particulatecomposition of the present invention with stirring, to slightlyacidified warm water, almost immediately produces an emulsion suitablefor use as a post-washing hair conditioner. The problems usuallyassociated with preparing formulations (e.g. incorporating aqueouspastes or dispersions of quaternary ammonium compounds along with otheringredients) are thereby eliminated.

A composition according to this invention may be obtained by meltingtogether a quaternary ammonium compound, a fatty alcohol, and analkylamido alkyldimethylamine, thoroughly mixing the molten materials,and then congealing the moltent mixture to form a particulate (e.g., byflaking). The particulate product thus obtained is a convenient means ofincorporating a quaternary ammonium compound into a hair care emulsionwithout the drawbacks usually associated with the preparation of suchemulsions.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a particulate composition which when added tostirred, heated, acidified water essentially instantly produces a stableemulsion suitable for use as a post-washing hair conditioner. Thequaternary ammonium compound contained in the composition of thisinvention is substantive to the hair. Quaternary ammonium compoundsuseful for the purposes of this invention may be produced by means wellknown to the art. It is well known in the art that tertiary amines maybe quaternized by such agents as benzylchloride, methyl chloride,dimethyl sulfate, and sodium chloroacetate. Virtually all tertiaryamines are amenable to quaternization, however, for the purposes of thisinvention at least one substituent of said tertiary amine should be along chain, (i.e.(fatty) alkyl, alkoxyl or alkylamido) group. Such fattyalkyl substituents are preferably mixtures of chain lengths of branchedand/or straight chain aliphatic moieties in the range of from about 10to about 20 carbons. These may be obtained by using amines derived fromnatural sources such as tallow, where the predominant chain lengths areC₁₆ and C₁₈, or other naturally occuring fats or oils with aliphaticchain lengths varying from about C₁₀ to about C₂₀, as is well known inthe art. Further, it is also well known in the art that methyl chloridemay be reacted with secondary amines in a mole ratio of 2:1 to producequaternary ammonium compounds use for hair conditioning. The quaternaryammonium compounds obtained by these methods and use for this inventionare of general formula: ##STR1## where R, R₁, R₂ and R₃ are C₁ -C₂₀branched or straight chain alkyl groups or mixtures thereof, and X⁻ isthe anionic residue of an alkylating agent. The preferred quaternaryammonium compounds of this invention may be prepared by the methodtaught by U.S. Pat. No. 3,803,137 by quaternization of a mixture ofstraight chain and branched chain amines as set forth in Example 1,below.

In order to obtain the composition of this invention an effective amountof said preferred quaternary ammonium compounds obtained as solids aremelted together with fatty alcohols and alkylamido alkyldimethylamines.Fatty alcohols may be derived from either natural or synthetic sources,and may have chain lengths from C₈ to C₂₂ or mixtures thereof. Thepreferred fatty alcohol of this invention is a mixture of 65 partsstearyl alcohol with 35 parts of cetyl alcohol (Adol 63; Sherex ChemicalCompany, Dublin, Ohio). Alkylamido alkyldimethylamines derived fromnaturally occuring and synthetically produced fatty acids may be usefulin this invention. Those derived from natural fats and oils have chainlength distributions from about C₈ to about C₂₂. The preferredalkylamido akyldimethylamine is stearamido propyldimethylamine. Thefatty alcohol functions as an emollient or lubricant, a combing aid andviscosity builder. The fatty alcohol, although not substantive to thehair, does coat it and provides some lubrication. The function of thealkylamido alkyldimethylamine is to provide both emulsion stabilizationand hair conditioning properties. The ingredients of the composition ofthis invention may be added to each other in any order. Thus, thepreferred composition of this invention may be prepared by meltingtogether 74 parts of the said preferred fatty alcohol with 20 parts ofthe said preferred quaternary ammonium compound and 5.8 parts of thesaid preferred alkylamido alkyldimethylamine, at about 80° C. Themixture was stirred until uniform, and cooled to approximately 50° C.,to obtain a friable solid. Cooling may, of course, be accomplished on achiller roll, chill belt or like device, whereby a particulate in theform of flakes may be obtained, as is well known in the art. Thequaternary ammonium compound, or mixtures thereof, should melt aboveapproximately 30° C., and the fatty alcohol or mixture of fatty alcoholsshould melt above about 50° C., in order to obtain a friable solid. Inorder to obtain a stable hair conditioning emulsion, 8 parts of theparticulate of this invention were admixed with water at approximately70° C., to which sufficient citric acid had been added to adjust the pHto approximately 4.5. Upon stirring, a stable emulsion, suitable for useas a post-washing hair conditioner, was, almost immediately, obtained.None of the difficulties inherent in the use of quaternary ammoniumcompounds as pastes or dispersions, or the problems associated with thepreparation of emulsions were encountered. Optional ingredients, e.g.perfume, coloring, may then be added to obtain a formulated product.

To further illustrate the efficacy of this invention the followingnon-limiting examples are set forth.

EXAMPLE 1

A mixture of quaternary compounds derived from a mixture of fattyalcohols was prepared according to the process set forth in U.S. Pat.No. 4,098,822. Thus, a mixture of fatty alcohols, consisting of equalparts of C12-C15 primary alcohols containing 20-25% methyl branchedisomers (Neodol 25; Shell Chemical Co.) and C16-C18 primary alcohols(Alfol 1618; Continental Oil Company), was charged to a reactor. Typicaldistribution for the alcohol mixture is set forth below; sc denotingstraight chain, b denoting branch chain isomers respectively.

    ______________________________________                                               isomer                                                                              weight %                                                         ______________________________________                                               C11   1.0                                                                     C12 sc                                                                              9.25                                                                    C12 b 3.10                                                                    C13 sc                                                                              9.40                                                                    C13 b 3.15                                                                    C14 sc                                                                              11.65                                                                   C14 b 3.55                                                                    C15 sc                                                                              7.35                                                                    C15 b 2.40                                                                    C16 sc                                                                              31.50                                                                   C18 sc                                                                              17.00                                                                   C20   0.50                                                             ______________________________________                                    

The alcohol mixture was sparged with a mixture of hydrogen and ammoniaat 180°-190° C. in the presence of nickel catalyst, water and ammoniabeing continuously removed during the course of the reaction. When thetotal nitrogen content was found to remain constant, requiringapproximately 6 hours, the sparge of gasses was stopped, and the reactorwas cooled to approximately 100° C. Vacuum was applied to removeresidual hydrogen, ammonia, and water. The reactor was then unsealed,and the product, predominantly di-fattyalkyl secondary amines filtered,to remove catalysts. Quaternization was accomplished by reacting of moleof said secondary amines dissolved in isopropanol with 2 moles of methylchloride, in a sealed, agitated reactor in the presence of concentrated(73%) aqueous sodium hydroxide. The temperature within the reactor wasmaintained at 90°-95° C., and methyl chloride was continuously added, soas to maintain the pressure at about 3 atmospheres, until the free aminecontent was less than 1.5% by weight. The reaction mixture was thencooled to about 55° C., diluted with isopropanol, and filtered to removebyproduct sodium chloride. A mixture of quaternary ammonium chlorides,predominantly dialkyldimethyl, was isolated by vacuum removal ofresidual water and isopropanol had the formulae: ##STR2## wherein R₁collectively represents the alkyl residue of a primary alcohol mixturecomposed of 30-70 wt. percent of (a) straight-chain C₁₆ -C₂₂ alcoholsand correspondingly from 70-30 wt. percent of (b) C₈ -C₁₅ Oxo alcoholsconsisting essentially of a mixture of straight-chain and single methylbranched isomers, and (a) and (b) being in relative proportions so thatfrom about 95-80 wt. percent of said R₁ groups are straight-chain alkyland correspondingly from 5-20 wt. percent are said branched alkyl, R isa C₁ -C₃ alkyl group, X⁻ represents a chloride, bromide or iodide anion,and wherein said mixture of quaternaries is essentially composed of 0-10wt. percent of compounds of Formula I, 60-85 wt. percent of compounds ofFormula II, and 5-25 wt. percent of compounds of Formula III.

The isolated mixture of quaternaryammonium compounds was found to meltat about 30° C. by melting on a Fisher-Johns melting apparatus, (FisherScientific Co., Pittsburgh, PA).

EXAMPLE 2

Twenty parts of the product of Example 1 were admixed with 74.2 parts ofa mixture consisting of (a) 65 parts of stearyl alcohol and 35 parts ofcetyl alcohol (Adol 63; Sherex Chemical Company, Dublin, Ohio), and (b)5.76 parts of stearamido propyldimethylamine. The molten mixture wasstirred until uniform, then poured out onto a flat sheet and allowed tocool to approximately 25° C. The resulting solid was then easily brokenup to obtain non-adhering flakes.

EXAMPLE 3

A hair conditioning emulsion was prepared by adding 8 parts of theparticulate product of Example 2(DPSC 131-130-1) to 92 parts of water at70°-80° C. which contained sufficient citric acid (approximately 0.5parts) to bring the pH to between 4 and 5. Upon stirring, an emulsionformed almost immediately. This emulsion was stored at room temperatureand appeared to be stable, i.e. did not separate with time.

EXAMPLE 4

A swatch of standard European human hair (Chicago Hair Goods, Chicago,Ill.) weighing 3.0 grams was washed with standard shampoo (i.e. asolution of sodium lauryl sulfate), and rinsed. To the wet washedswatch, 0.5 ml. of the product of Example 3 was applied, and worked intothe hairswatch. The swatch was then rinsed with warm water (30°-40° C.),drip dried and set up on hair rollers. The rolled hair swatches wereallowed to dry at ambient conditions (20° C., 50% relative humidity).When dry, the rollers were taken down and the swatches were combed out.When compared with swatches of standard hair which were not treated withthe product of Example 3, noticeable differences were observed. Theuntreated hair did not comb evenly, supported a static charge, wascoarse to the touch, brittle and appeared dull. The swatches treatedwith the product of Example 3, on the other hand, were glossy, combedeasily, and did not support static charges.

EXAMPLE 5

The product of Example 2 (DPSC 131-130-1) was formulated into twodifferent preparations which are each imitative of a commerciallyavailable post-washing hair care product. Thus, the procedure of Example3 was followed to produce an emulsion to which additional ingredientswere added. The respective formulations are set forth in the tablebelow.

    ______________________________________                                                       SC-179-170-I                                                                             SC-179-170-II                                       Formulation    (Parts)    (Parts)                                             ______________________________________                                        DP SC 131-130-1                                                                              5.0        5.0                                                 Citric Acid    qs pH 4.5  qs pH 4.5                                           Germicide      0.3        0.3                                                 Propylene Glycol                                                                             --         0.3                                                 Silicone       --         0.3                                                 Perfume        0.1        0.1                                                 Water          94.6       94.0                                                ______________________________________                                    

A blank, that is, a composition imitative of a post-washing hair careproduct, but containing no hair conditioning composition was formulatedby mixing the ingredients set forth in the table below:

    ______________________________________                                                           SC 155-156                                                 Blank Formulation  (parts)                                                    ______________________________________                                        Polyacrylic emulsifier                                                                           0.3                                                        Polyethylene glycol with                                                      an average mol. wt. of 6000                                                                      0.1                                                        Perfume            0.2                                                        NaOH               0.12                                                       Water              99.28                                                      ______________________________________                                    

Formulation SC 179-170-I was evaluated against the blank (SC 155-156,and against a commercially available hair conditioning emulsioncontaining similar ingredients, designated as Control I. Formulation SC179-170-II was evaluated against a commercially available hairconditioning emulsion containing silicone, propylene glycol, and othersimilar ingredients, designated as Control II. Each formulation wasblind coded so as to preclude bias by either cosmetologist or panelist.Evaluations were conducted on separate panels of eight volunteers each,randomly selected for age, sex, and hair type. Thus, the panelists hadtheir hair shampooed and treated by a licensed, professionalcosmetologist, under beauty salon conditions. Each test subject's hairwas shampooed twice with the same commercially availablenon-conditioning shampoo. For the first washing, 3 ml. of shampoo wasapplied, lathered and thoroughly rinsed. The hair was again washed using2 ml. of shampoo, and then thoroughly rinsed. The set hair was dividedinto right and left halves from forehead to the back of the neck. Four(4) ml. of a test hair care formulation was applied to one side of thehead, and 4 ml. of either a control or blank formulation was applied tothe other. The formulations were individually, manually washed into thehair carefully so as not to mix the two sides, and let stand for 2minutes. Each side was individually rinsed for 10 seconds to determinerinsibility, i.e. ease of removal. Each half of the head was thenthoroughly rinsed. A comb was passed through each side simultaneously toevaluate resistance and detangling. Combing was continued to evaluatewet combability. The hair was then dryed with a salon dryer and combedagain to evaluate dry combability, and the other criteria set forth inthe evaluation table below.

The fingers were run through the hair to evaluate "feel." The datatabulated below are evaluations by the professional cosmetologist whoperformed each salon test. Certain criteria were subjectively evaluatedby each panelist. Each criterion was rated on a scale of 1 to 6, 6 beingthe best. The scores for each half of a head of hair were summed, thenaveraged. The data presented in Table I below are the percentage scoresfor each criterion, as evaluated by the professional cosmetologist. Thedefinitions of the evaluation criteria follow the table.

                                      TABLE I                                     __________________________________________________________________________    Average Percentage Score in Salon Evaluation                                  of Hair Conditioning Formulations                                             (Cosmetologist's Evaluation)                                                                 Blank         Control    Control                                       SC-179-170-I                                                                         (SC155-156)                                                                          SC-179-170-I                                                                         I   SC-179-170-II                                                                        II                                    __________________________________________________________________________    Rinsibility*                                                                          74     26     36     64  60     31                                    Detangling                                                                            74     26     47     53  53     47                                    Wet Comb                                                                              77     23     59     41  58     42                                    Dry Comb                                                                              75     25     67     23  42     58                                    Static  67     33     42     58  68     32                                    Feel    82     18     65     35  50     50                                    Manageability                                                                         78     22     52     48  40     60                                    Body    81     19     57     43  66     34                                    Shine   79     21     45     58  59     41                                    Curl Retention                                                                        79     21     45     55  68     32                                    __________________________________________________________________________     *Criteria are defined as:                                                     Rinsibility: The ability of the product to rinse and leave the hair           feeling clean yet conditioned.                                                Detangling: The products performance as an aid in reducing tangles in the     hair.                                                                         Wet Comb: Resistance of hair to combing when wet.                             Dry Comb: Same as Wet Comb but after the hair has been styled and dried.      Static: The relative reduction of static flyaway.                             Feel: How soft and silky the product leaves the hair.                          Manageability: How well the hair behaves when styled.                        Body: The fullness of the hair after it is dry.                               Shine: The comparative shine or sheen of the two products.                    Curl Rentention: How well the hair holds its style over time.            

The individual panelists also reported their subjective evaluations ofcertain of the criteria within 24 hours after salon evaluations. Thesescores were summed and the average values obtained are reported in TableII below.

                                      TABLE II                                    __________________________________________________________________________    Average Percentage Score in Salon Evaluation of                               Hair Conditioning Formulations                                                (Panelist's Evaluation)                                                               Blank         Control       Control                                   SC-179-170-I                                                                          (SC155-156)                                                                          SC-179-170-I                                                                         I    SC-179-170-II                                                                          II                                        __________________________________________________________________________    Static  50     50     48   52     53                                                                              47                                        Feel    45     55     51   49     53                                                                              47                                        Dry Comb                                                                              46     54     45   55     54                                                                              46                                        Body    45     55     55   45     52                                                                              48                                        Shine   53     47     51   49     56                                                                              44                                        Curl Retention                                                                        57     43     53   47     50                                                                              50                                        __________________________________________________________________________     *Criteria defined as above.                                                   **The time elapsed between salon treatment and panelist evaluations           permitted the reabsorption of moisture and natural oils by the hair,          resulting in little descrimination among the materials evaluated.        

It is evident from the data on Tables I and II, above, that thepost-washing hair care formulations obtained from the emulsifiableparticulate composition of this invention are at least as effective asthe commercially prepared hair care emulsions with which they werecompared.

We claim:
 1. A particulate emulsifiable hair conditioning compositioncomrising: (a) from 40-80% by weight of aliphatic alcohol of 8 or morecarbons, or mixtures thereof; and (b) from 20-60% of a quaternaryammonium compound or mixtures thereof miscible with said alcoholmixture; and (c) from 2-10% of a fatty alkylamido alkyldialkylamine ofthe general formula ##STR3## where; n is 1-6R₁ is C8 to C28 alkyl group,R₂ is a C1 to C5 alkyl group; such that said composition melts at orabove 30° C.
 2. The composition as in claim 1 where the aliphaticalcohol is a mixture of 50-80% stearyl alcohol with up to 50% cetylalcohol.
 3. The composition as in claim 2 where the aliphatic alcohol isa mixture of 65% stearyl alcohol and 35% cetyl alcohol.
 4. Thecomposition as in claim 2 where the quaternary ammonium compound is ofthe general formula: ##STR4## where: R₁ is a C₆ -C₂₂ alkyl groupR₂ is aC₁ -C₃ alkyl group R₃ is a C₁ -C₃ alkyl group, a benzyl group, or aphenyl group m is 1-6, X⁻ is the monovalent anionic residue of analkylating agent.
 5. The composition as in claim 2 where the quaternaryammonium compound is of general formula ##STR5## where: R₁ and R₂ are C₈-C₁₈ alkyl groups,R₃ is a C₁ -C₃ alkyl group, R₄ is a C₁ -C₃ alkylgroup, a phenyl group or a benzyl group, X⁻ is the monovalent cationresidue from alkylating agent.
 6. The composition as in claim 3 wherethe quaternary ammonium compound consists of a mixture of quaternaryammonium compounds having the formulae ##STR6## wherein R₁ collectivelyrepresents the alkyl residue of a primary alcohol mixture composed of30-70 weight percent of (a) straight chain C₁₆ -C₂₂ alcohols andcorrespondingly from 70-30 weight % of (b) C₈ to C₁₅ oxoalcoholsconsisting essentially of a mixture of straight chain and single methylbranched isomers, said (a) and (b) being in relative proportions so thatfrom about 95-80 weight percent of said R₁ groups are straight chainalkyl and correspondingly from 5-20 weight percent are said branchedalkyl, R is a C₁ to C₃ alkyl group, X represents a chloride, bromide, oriodide anion, and wherein said mixture of quaternaries is essentiallycomposed of 0-10 weight percent of compounds of formula I, 60-85 weightpercent of compounds of formula II, and 5-25 weight percent of compoundsof formula III.
 7. The composition as in claim 6 where X is chloride. 8.The composition as in claim 7 where the fatty alkylamidoalkyldialkylamine is such that R₁ is predominantly a C₁₇ alkyl group, nis 3, and R₂ is a methyl group.
 9. The composition as in claim 8 wherethe aliphatic alcohol mixture is present in 70-80% by weight, thequaternary ammonium compound is present in 10-30% by weight.